JP2017113709A - Surfactant carrier - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a surfactant carrier having great abilities to absorb and retain a surfactant.SOLUTION: A surfactant carrier has a surfactant absorbing performance of 10 times or more.SELECTED DRAWING: None

Description

The present invention relates to a carrier capable of carrying a surfactant. More specifically, the present invention relates to a carrier that can absorb and carry a surfactant.

Surfactants are used as various agents such as detergents and cleaning agents. Since these are excellent in usability, liquids tend to be preferred. However, for example, liquid detergents may spill and adhere to floors or equipment when used in small portions from containers. In such a case, usually a certain part is absorbed by paper, waste cloth, sawdust, etc., and the remaining part is wiped dry, rinsed with a large amount of water, or wiped with a mop wet with water many times. Remove the dripping.
However, paper, waste, and sawdust do not have a sufficient ability to absorb surfactants, and even if wiped with water or wiped with water, the surface area of the surfactant is increased, but it is difficult to remove completely. There are many cases that cannot be used.

On the other hand, for example, Patent Document 1 discloses a support material that supports a surfactant,
General formula (1)
_{CH 2 = CR-CO- (X} ) n -Y ...... (1)
(In the formula, R represents a hydrogen atom or a methyl group, X represents an oxyalkylene group having 2 to 4 carbon atoms in which the molar fraction of the oxyethylene group to the total oxyalkylene group is 50% or more, and Y represents , An alkoxy group having 1 to 5 carbon atoms, a phenoxy group, or an oxyalkylphenyl group having 1 to 3 alkyl groups having 1 to 9 carbon atoms as a substituent, and n is an integer of 3 to 100 on average A surfactant support material characterized by containing a cross-linked polymer obtained by polymerizing a monomer component containing a (meth) acrylic acid ester monomer represented by . In Patent Document 1, the above-mentioned support material gels and supports the surfactant, has excellent shapeability when supported, and has a property of gradually releasing the surfactant (sustained release). In other words, by supporting the surfactant on the support material, it is possible to improve the usability when using the surfactant as a detergent, for example, so that cleaning and cleaning can be performed quickly and easily. It is disclosed that there is an effect of being able to.

Further, for example, in Patent Document 2, 0.5 to 10% by weight with respect to N-vinylpyrrolidone, at least two ethylenically unsaturated groups having at least one of them bonded to an amide nitrogen atom. Of polyvinylpyrrolidone by allowing the polymerization of N-vinylpyrrolidone to proceed in the presence of a cyclic amide and initiating the reaction on the surface of the metal without passivating and forming a transparent oxide layer A method for manufacturing a body is disclosed. According to the above method, it is disclosed that a crosslinked product of polyvinylpyrrolidone that is insoluble and has low swelling property can be obtained.

Further, Patent Document 3 discloses that a polymerizable monomer component containing N-vinylpyrrolidone obtained without using N-vinylpyrrolidone or acetylene having a γ-butyrolactone content of 500 ppm or less as a raw material is polymerized. It is disclosed that a vinylpyrrolidone-based polymer having a desired molecular weight, a small amount of residual monomer, and capable of exhibiting excellent performance even when crosslinked to form a water-absorbent resin, for example, is disclosed.

JP-A-9-157327 JP 47-11497 A Japanese Patent Laid-Open No. 2001-226431

As described above, the surfactant is conveniently used in a liquid form, but when the surfactant adheres to an unfavorable place, the removal thereof is complicated. Therefore, in order to improve the removal operation of the surfactant, there has been a demand for a material excellent in the liquid absorption performance of the surfactant.
An object of the present invention is to provide a surfactant-carrying agent that is excellent in the ability to absorb and retain a surfactant.

The present inventors have intensively studied to solve the above problems. As a result, the present inventors have found that a crosslinked polymer having a specific structural unit has a good surfactant adsorption ability and retention ability, and has completed the present invention.

That is, the surfactant-carrying agent of the present invention is a surfactant-carrying agent having a surfactant absorption capacity of 10 times or more.

The present invention is also a surfactant-supporting agent comprising a cyclic N-vinyl lactam-based crosslinked product, wherein the cyclic N-vinyl lactam-based crosslinked product has 50 to 100 mol% of structural units derived from N-vinyl lactam. .

The surfactant-carrying agent of the present invention has a good surfactant-absorbing ability. Therefore, it can be preferably used for removing the dripping surfactant. The surfactant-carrying agent of the present invention can also be used as a dispersant or a thickener in cosmetic applications.

Hereinafter, the present invention will be described in detail.

The surfactant-carrying agent of the present invention is characterized in that the surfactant-absorbing ability is 10 times or more, and thus can be suitably used as a material for removing the surfactant. The surfactant-absorbing ability of the surfactant-carrying agent of the present invention is preferably 15 times or more, and more preferably 20 times or more.
The surfactant absorbing capacity is a value calculated by “(weight of supporting agent + amount of surfactant absorbed) / weight of supporting agent”.

<Cyclic N-vinyl lactam crosslinked product>
The first surfactant-carrying agent of the present invention (hereinafter referred to as “surfactant-carrying agent (I) of the present invention”) is a cyclic N-vinyllactam-based crosslinked product (hereinafter referred to as “crosslinked product of the present invention (I)”). ").

In the present invention, “cyclic N-vinyl lactam cross-linked product” means (i) a cross-linked product having a structural unit derived from N-vinyl lactam (hereinafter also referred to as cross-linked product (I-1) of the present invention), (Ii) A crosslinked product (hereinafter also referred to as a crosslinked product (I-2) of the present invention) obtained by polymerizing a monomer component containing N-vinyl lactam.

The above “structural unit derived from N-vinyl lactam” represents a structural unit having the same structure as the structural unit formed by polymerizing N-vinyl lactam. That is, if it has the same structure as the structural unit formed by polymerizing N-vinyl lactam, the structural unit formed by a method other than the method for polymerizing N-vinyl lactam is also a structure derived from N-vinyl lactam. Included in the unit.

The “N-vinyl lactam” is not limited as long as it is a monomer having a cyclic N-vinyl lactam structure. For example, N-vinyl pyrrolidone, N-vinyl piperidone, N-vinyl caprolactam, and 1 or contained therein Examples thereof include compounds in which two or more hydrogen atoms are substituted with other substituents. Examples of the other substituent include an alkyl group, an aryl group, a hydroxyl group, an alkoxy group, a carbonyl group, a carboxyl group, and an amide group. The other substituent is preferably a substituent having 0 to 12 carbon atoms, and more preferably a substituent having 1 to 4 carbon atoms. These cyclic N-vinyl lactam monomers may be used alone or in combination of two or more. Among the cyclic N-vinyl lactam monomers, the surfactant-supporting agent has a tendency to improve the liquid absorption ability, so that one or two or more hydrogen atoms contained in N-vinyl pyrrolidone and N-vinyl pyrrolidone are others. Particularly preferred are compounds substituted with these substituents.

The crosslinked product (I) of the present invention preferably has a structural unit derived from N-vinyl lactam (the crosslinked product (I-1) of the present invention essentially has a structural unit derived from N-vinyl lactam). , With respect to 100 mol% of structural units derived from N-vinyl lactam as structural units derived from all monomers (structural units derived from N-vinyl lactam and structural units derived from other monomers described later). 50 mol% or more and 100 mol% or less is more preferable, 60 mol% or more and 100 mol% or less is more preferable, 70 mol% or more and 100 mol% or less is particularly preferable.

The structural unit derived from N-vinyl lactam can be represented by the following structural formula, for example, when N-vinyl lactam is N-vinyl pyrrolidone.

In the general formula (1), the asterisk mark represents an atom to which a structural unit derived from N-vinyl lactam is bonded.

The crosslinked body (I) of the present invention may have a structural unit derived from another monomer. The above-mentioned other monomer is a compound having only one polymerizable carbon-carbon double bond in the structure, and N-vinyl lactam and a crosslinking monomer described later are included in the other monomers. I can't. The other monomers are preferably radically polymerizable compounds.
Specific examples of the other monomers include (i) unsaturated monocarboxylic acids such as acrylic acid and methacrylic acid and their salts; (ii) fumaric acid, maleic acid, methylene glutaric acid, itaconic acid. Unsaturated dicarboxylic acids such as these and their salts (which may be mono- or di-salts); (iii) 3-allyloxy-2-hydroxypropane sulfonic acid, (meth) allyl sulfonic acid, isoprene sulfonic acid (Iv) hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, 3- (meth) allyloxy-1,2-dihydroxypropane, (meth) allyl alcohol, isoprenol, etc. Unsaturated alcohols and alkylene oxide adducts obtained by adding alkylene oxides to these hydroxyl groups; ) (Meth) acrylate esters such as methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, cyclohexyl (meth) acrylate; (vi) (meth) acrylamide, N-monomethyl ( (Meth) acrylamide, N-monoethyl (meth) acrylamide, N-substituted or unsubstituted (meth) acrylamide such as N, N-dimethyl (meth) acrylamide; (vii) vinylaryl monomers such as styrene, indene and vinylaniline (Viii) alkenes such as ethylene, propylene, butadiene, isobutylene and octene; (ix) vinyl carboxylates such as vinyl acetate and vinyl propionate; (x) N, N-dimethylaminoethyl (meth) acrylate, N , N-Dimethylaminoethyl (meth) acrylamide (Xi) vinylamides such as vinylformamide, vinylacetamide, vinyloxazolidone; (xii) maleic anhydride, itaconic anhydride, etc. (Xiii) vinyl ethylene carbonate and derivatives thereof; (xiv) ethyl (meth) acrylate-2-sulfonate and derivatives thereof; (xv) vinyl ethers such as methyl vinyl ether, ethyl vinyl ether, butyl vinyl ether, and the like. Can be mentioned.
Among these, the monomers (i) to (x) are preferable, and the monomers (i), (vi), (vii), (ix), and (x) are more preferable.
Examples of the salts in the above (i) to (iii) and (x) include metal salts, ammonium salts, organic amine salts and the like. Examples of the alkylene oxide in the above (iv) include ethylene oxide, propylene oxide and the like, preferably an alkylene oxide having 1 to 20 carbon atoms, more preferably an alkylene oxide having 1 to 4 carbon atoms. As addition mole number of the alkylene oxide in said (iv), 0-50 mol is preferable with respect to 1 mol of compounds of said (iv), and 0-20 mol is more preferable.

As said other monomer, a C2-C20 monomer is preferable. More preferably, it is a C2-C15 monomer, More preferably, it is a C2-C10 monomer. In addition, when other monomers are alkylene oxide adducts, it is preferable that carbon number of structural parts other than an alkylene oxide structural part is these values.

When the crosslinked product (I) of the present invention has a structural unit derived from another monomer, it may have one type of structural unit derived from another monomer or two or more types. May be. The structural unit derived from the other monomer is a structural unit having the same structure as the structural unit formed by polymerization of the other monomer, specifically, the polymerizable unit of the other monomer. It is a structure in which a carbon-carbon double bond is a single bond. For example, when the other monomer is butyl acrylate (CH ₂ ═CHCOOC ₄ H ₉ ), the structural unit derived from the other monomer is —CH ₂ —CH (COOC ₄ H ₉ ) —. Can be represented.

In the crosslinked product (I) of the present invention, the content ratio of structural units derived from other monomers is 0 mol% or more and 50 mol% with respect to 100 mol% of structural units derived from all monomers. It is preferably 0 mol% or more and 40 mol% or less, more preferably 0 mol% or more and 30 mol% or less.

The crosslinked body (I) of the present invention has a crosslinked structure in the structure. When the crosslinked product (I) of the present invention has a crosslinked structure in the structure, (1) When a polymer having a crosslinked structure is produced by polymerizing a monomer component containing the following crosslinkable monomer (2) A polymer obtained by polymerizing a monomer component containing a monomer having a reactive functional group is cross-linked by reacting a cross-linking agent having a plurality of functional groups that react with the reactive functional group. When forming a structure, (3) a monomer that includes both a monomer 1 having a reactive functional group and a monomer 2 having a reactive functional group that reacts with the reactive functional group that the monomer 1 has. When the monomer component is polymerized, the reactive functional group of the monomer 1 and the reactive functional group of the monomer 2 are reacted to form a crosslinked structure (self-crosslinking). When a radical is generated and a crosslinked structure is formed between the polymers in which the radical is generated (self-crosslinking), (5) Produced was, may form a crosslinked structure by reacting the polymer and below the crosslinking monomer radicals occurs.
The crosslinked structure (I) of the present invention may be formed by any one of the above (1) to (5), but is preferably formed by (1) above.

As above-mentioned, it is preferable that the crosslinked body (I) of this invention has a structural unit derived from a crosslinkable monomer. In the present invention, the crosslinkable monomer is a compound having at least two polymerizable carbon-carbon double bond groups per molecule, preferably at least two radical polymerizable carbon carbons per molecule. It is a compound having a double bond group.
Specific examples of the crosslinkable monomer include N, N′-alkylenebis (meth) acrylamide having an alkylene group having 1 to 4 carbon atoms such as N, N′-methylenebis (meth) acrylamide; (Poly) ethylene glycol di (meth) acrylate, (poly) propylene glycol di (meth) acrylate and other (poly) alkylene glycol di (meth) acrylates having a C 1-4 alkylene group; trimethylolpropane tri (meta ) Trimethylolpropane (di, optionally modified with alkylene oxide having 1 to 4 carbon atoms such as acrylate, trimethylolpropane di (meth) acrylate, ethylene oxide modified trimethylolpropane tri (meth) acrylate, etc. Tri) (meth) acrylate; grease Glycerin (di, tri) (meth) acrylates such as phosphorus tri (meth) acrylate and glycerin acrylate methacrylate; Pentaerythritol (di, tri, tetra) (meth) acrylates such as pentaerythritol tetra (meth) acrylate; Dipentaerythritol hexa ( Dipentaerythritol (di, tri, tetra, penta, hexa) (meth) acrylate such as (meth) acrylate; Pentaerythritol (di, tri, tetra) (meth) such as pentaerythritol tri (meth) allyl ether Allyl ether; triallyl cyanurate (triallyl cyanurate), triallyl isocyanurate, triallyl phosphate, triallylamine and other C9-20 triallyl compounds; diallyl carbonate, 1,3-bis (allyloxy) ) Diallyl compounds having 6 to 20 carbon atoms such as 2-propanol; (di, tri) vinyl compounds having 4 to 20 carbon atoms such as divinyl ether, divinyl ketone and trivinylbenzene; such as tolylene diisocyanate and hexamethylene diisocyanate. Examples thereof include diisocyanates having 2 to 20 carbon atoms; poly (meth) allyloxyalkanes and the like. These may use only 1 type and may use 2 or more types together.
Among the crosslinkable monomers, it is preferable to use a compound having two or more allyl groups because the remaining cyclic N-vinyl lactam monomer and the soluble component tend to decrease. Specifically, triallyl cyanurate, triallyl isocyanurate, triallyl phosphate, triallylamine, diallyl carbonate, 1,3-bis (allyloxy) -2-propanol, pentaerythritol (di, tri, tetra) (meth) allyl Ethers are preferred, and triallyl cyanurate and pentaerythritol (di, tri, tetra) (meth) allyl ether are most preferred.

The polyalkylene glycol di (meth) acrylate preferably has 2 or more and 50 or less, more preferably 2 or more and 20 or less, and further preferably 2 or more and 10 or less oxyalkylene groups per molecule. It is preferable that an oxyethylene group is 50-100 mol% with respect to 100 mol% of oxyalkylene groups which the said polyalkylene glycol di (meth) acrylate has, and it is preferable that it is 80-100 mol%.
One molecule of trimethylolpropane (di, tri) (meth) acrylate when the above trimethylolpropane (di, tri) (meth) acrylate is modified with an alkylene oxide having an alkylene group having 1 to 4 carbon atoms It is preferable that the average number of added alkylene oxides is the same.

The structural unit derived from the crosslinkable monomer is a structural unit having the same structure as a structural unit in which at least one of the polymerizable carbon-carbon double bond groups of the crosslinkable monomer is a single bond. is there. That is, if the crosslinkable monomer has the same structure as the structural unit in which at least one of the polymerizable carbon-carbon double bond groups is a single bond, for example, a monomer other than the crosslinkable monomer may be used. The structural unit formed by post-crosslinking after polymerization is also included in the structural unit derived from the crosslinkable monomer.

There is no restriction | limiting in particular about the usage-amount of the said crosslinkable monomer, What is necessary is just to adjust suitably according to the intended purpose. For example, in the crosslinked product (I) of the present invention, the structural unit derived from the crosslinkable monomer is 0.0001 mol% or more and 10 mol% or less with respect to 100 mol% of the structural unit derived from all monomers. It is preferable to have 0.01 mol% or more and 1 mol% or less.
By adjusting the usage-amount of a crosslinkable monomer, the ability to absorb and hold | maintain surfactant and a solvent which the crosslinked body (I) of this invention has can be adjusted. When the crosslinked product (I) of the present invention absorbs a solvent and swells and gels, the crosslinked product (I) of the present invention can be expected to exhibit an effect as a thickener, Moisturizing effect can also be expected by absorbing, holding, and releasing water.

When the crosslinked product (I) of the present invention has a crosslinked structure formed by the above (2) or (3), the crosslinked product (I) of the present invention is a structural unit derived from the above-mentioned other monomers. As described above, it has a structural unit derived from a monomer having a reactive functional group.
Examples of reactive functional groups include carboxyl groups, sulfonic acid groups, and esters and salts thereof; amino groups, hydroxyl groups, and the like.
When the cross-linked structure of the cross-linked product (I) of the present invention is formed by the above (3), the combination of reactive functional groups having reactivity with each other includes a carboxyl group (and its ester or salt) and Examples thereof include a hydroxyl group, a sulfonic acid group (and ester or salt thereof) and a hydroxyl group, a carboxyl group (and ester or salt thereof) and an amino group, a sulfonic acid group (and ester or salt thereof) and an amino group. When the cross-linked structure of the cross-linked product (I) of the present invention is formed by the above (2), the reactive functional group possessed by the monomer and the functionality that reacts with the reactive functional group possessed by the cross-linking agent The example of the combination of groups is the same as this.

When the cross-linked product (I) of the present invention has a cross-linked structure formed by the above (2) or (3), reactive functional groups for 100 mol% of all structural units of the cross-linked product (I) of the present invention are present. The proportion of the structural unit derived from the monomer it has is preferably 0.0002 mol% or more and 20 mol% or less, and more preferably 0.02 mol% or more and 2 mol% or less.

The crosslinked product (I) of the present invention is not particularly limited, but preferably has an average particle size of 0.1 μm or more and 100 μm or less. More preferably, they are 0.1 micrometer or more and 80 micrometers or less, More preferably, they are 0.1 micrometer or more and 50 micrometers or less. By being in the above range, the surfactant-absorbing ability of the surfactant-carrying agent of the present invention tends to be improved.
The average particle size of the crosslinked product can be measured by the method described in Example 1.

<Method for producing crosslinked body>
Although the manufacturing method of the crosslinked body (I) of this invention is arbitrary, it manufactures with the manufacturing method including the process (henceforth a "polymerization process") of superposing | polymerizing the monomer component containing N-vinyl lactam. Is preferable (the crosslinked product (I-2) of the present invention is produced by including the above-mentioned polymerization step).

The polymerization in the polymerization step may be performed in the absence of a solvent, or a solvent may be used. The polymerization may be performed by various conventionally known methods such as bulk polymerization, solution polymerization, suspension polymerization, reverse phase suspension polymerization, emulsion polymerization, reverse phase emulsion polymerization, precipitation polymerization, or cast polymerization. A thin film polymerization method, a spray polymerization method, or the like can be employed. The stirring method for carrying out the polymerization reaction is not particularly limited, but when a gel-like cross-linked product is produced, a double-arm kneader is used as a stirring device, and the shear of the double-arm kneader is used. It is more preferable to stir while subdividing by force. The polymerization step can be carried out either batchwise or continuously.

In the polymerization step, polymerization of the monomer component containing N-vinyl lactam can be initiated by adding a polymerization initiator, irradiating UV, applying heat, or light in the presence of a photoinitiator. The method etc. which irradiate can be employ | adopted.

In the polymerization step, when a solvent is used, examples of the solvent include one or more selected from water, methyl alcohol, ethyl alcohol, isopropyl alcohol, n-butyl alcohol, diethylene glycol, and other alcohols. .

In performing the polymerization in the polymerization step, it is preferable to use a polymerization initiator. Examples of the polymerization initiator include peroxides such as hydrogen peroxide and t-butyl hydroperoxide; persulfates such as sodium persulfate, potassium persulfate, and ammonium persulfate; dimethyl 2,2′-azobis (2 -Methylpropionate), 2,2'-azobis (isobutyronitrile), 2,2'-azobis (2-methylbutyronitrile), 2,2'-azobis (2-methylpropionamidine) dihydrochloride Salt, 2,2′-azobis [N- (2-carboxyethyl) -2-methylpropionamidine] hydrate, 2,2′-azobis [2- (2-imidazolin-2-yl) propane], 2 , 2′-azobis [2- (2-imidazolin-2-yl) propane] dihydrochloride, 2,2′-azobis [2- (2-imidazolin-2-yl) propane] disulfate hydrate, , 2′-azobis (1-imino-1-pyrrolidino-2-methylpropane) dihydrochloride, 2,2′-azobis [N- (2-carboxyethyl) -2-methylpropionamidine] n hydrate, Azo compounds such as 2,2′-azobis [2-methyl-N- (2-hydroxyethyl) propionamide]; benzoyl peroxide, lauroyl peroxide, peracetic acid, di-t-butyl peroxide, cumene hydroper Organic peroxides such as oxides; redox that generates radicals by combining oxidizing agents and reducing agents, such as ascorbic acid and hydrogen peroxide, sodium sulfoxylate and t-butyl hydroperoxide, persulfate and metal salts A mold initiator or the like is preferred. Of these polymerization initiators, hydrogen peroxide, persulfate, and azo compounds are preferable, and azo compounds are most preferable. Among them, 2,2′-azobis [2- (2-imidazolin-2-yl) propane] dihydrochloride, 2,2′-azobis [2- (2-imidazolin-2-yl) propane], 2,2 '-Azobis [2- (2-imidazolin-2-yl) propane] disulfate hydrate, 2,2'-azobis (2-methylpropionamidine) dihydrochloride, 2,2'-azobis (2-methyl) Butyronitrile) is more preferred. These polymerization initiators may be used alone or in the form of a mixture of two or more.

The amount of the polymerization initiator used is 0.1 g with respect to 1 mol of the monomer used (total amount of N-vinyl lactam, other monomers and crosslinkable monomers described above). It is preferably 10 g or less, more preferably 0.1 g or more and 7 g or less, and further preferably 0.1 g or more and 5 g or less.
By making the usage-amount of an initiator into such a ratio, the ratio of the unreacted monomer contained in the polymer obtained can be fully reduced.

The polymerization step is preferably performed in the presence of the crosslinkable monomer. In that case, the usage-amount of the crosslinkable monomer in the said polymerization process does not have a restriction | limiting in particular, What is necessary is just to adjust suitably according to the intended purpose. For example, it is preferable to have 0.0001 mol% or more and 10 mol% or less, and 0.01 mol% or more and 1 mol% with respect to 100 mol% of the total amount of N-vinyllactam and other monomers described above. It is more preferable to have the following.

The amount of N-vinyl lactam used in the polymerization step is preferably 50 mol% or more and 100 mol% or less, and 60 mol% or more and 100 mol% or less with respect to 100 mol% of all monomers. Is more preferably 70 mol% or more and 100 mol% or less. The amount of other monomers used in the polymerization step is preferably 0 mol% or more and 50 mol% or less, and is 0 mol% or more and 40 mol% or less with respect to 100 mol% of all monomers. More preferably, it is 0 mol% or more and 30 mol% or less.

In the polymerization step, as a suitable dispersant when employing the reverse phase suspension polymerization method, specifically, for example, sorbitan fatty acid ester, sucrose fatty acid ester, glycerin fatty acid ester, polyglycerin fatty acid ester, ethyl cellulose, Examples thereof include cellulose esters such as cellulose acetate, cellulose ethers, and carboxyl group-containing polymers such as α-olefin-maleic anhydride copolymers. These dispersants may be used alone or in combination of two or more. In addition, the hydrophobic organic solvent provided when employing the reverse phase suspension polymerization method is not particularly limited.

In the polymerization step, the polymerization temperature is not particularly limited, but a relatively low temperature is preferable because the molecular weight of the crosslinked product is increased, and the polymerization rate is further improved within the range of 20 ° C to 100 ° C. preferable. The reaction time may be appropriately set according to the reaction temperature, the type (property) and combination of the monomer component, the polymerization initiator, and the solvent, the amount used, etc. so that the polymerization reaction is completed. Good.

The material of the reaction vessel for performing the polymerization step is not particularly limited as long as the polymerization step can be performed, but it is preferable to use a reaction vessel made of a material such as stainless steel. By carrying out the polymerization reaction using a reaction vessel made of a material that easily transmits heat, the polymerization reaction proceeds sufficiently, and the unreacted monomer (such as N-vinyl lactam) contained in the resulting polymer is contained. The amount can be reduced.
It is also preferable to use a reaction vessel made of a material such as polypropylene that does not elute iron. By using a reaction vessel made of these materials, the content of iron contained in the resulting polymer can be reduced.

The crosslinked product of the present invention may be produced by including an optional step in addition to the polymerization step. For example, a drying step, a pulverizing step, a classification step, a granulation step, a post-crosslinking step, and the like may be included.

When the crosslinked product (I) of the present invention is obtained by polymerization using a solvent and is in a gel form, that is, a gel-like crosslinked body containing a solvent, the step of drying the gel-like crosslinked body is performed. It is preferable to provide it. In the present invention, drying refers to an operation of increasing the solid content. Usually, the ratio of the solid content relative to the weight of the entire crosslinked body may be increased as compared with that before drying, but preferably the weight of the entire crosslinked body is 100. The solid content is preferably increased to 95% by mass or more, more preferably 96% by mass or more with respect to mass%. In addition, it is preferable that the upper limit of solid content is about 99 mass%. Drying may be performed at the same time as polymerization, and drying during polymerization and drying after polymerization may be used in combination, but more preferably, a drying step of drying using a drying apparatus after polymerization is provided. Here, the solid content of the crosslinked product refers to a value measured by a measurement method described later.

The drying step is preferably performed in the range of 80 ° C. to 250 ° C. through 50% or more of the entire time of the drying step, more preferably through substantially all the drying steps. By being the said range, it exists in the tendency for various physical properties of a crosslinked body to improve more.
The drying temperature is defined by the heat medium temperature, but if it cannot be defined by the heat medium temperature such as microwave, it is defined by the material temperature. The drying method is not particularly limited as long as the drying temperature is within the above range, and hot air drying, airless drying, reduced pressure drying, infrared drying, microwave drying and the like can be suitably used. Among these, it is more preferable to use hot air drying. The amount of drying air when hot air drying is used is preferably 0.01 to 10 m / sec, more preferably 0.1 to 5 m / sec. The range of the drying temperature is more preferably 110 ° C to 220 ° C, and further preferably 120 ° C to 200 ° C. The drying may be performed at a constant temperature or may be performed by changing the temperature. However, it is preferable that substantially all the drying steps are performed within the above temperature range.

The pulverization step is preferably performed using a pulverizer. When the production method of the present invention includes a drying step, pulverization may be performed before, during or after drying, but preferably after drying. The pulverizer is not particularly limited. For example, a roll pulverizer such as a roll mill, a hammer pulverizer such as a hammer mill, an impact pulverizer, a cutter mill, a turbo grinder, a ball mill, a flash mill, and a jet. A mill or the like is used. Among these, it is more preferable to use a roll mill in order to control the particle size distribution. In order to control the particle size distribution, it is more preferable to pulverize continuously twice or more, and it is more preferable to pulverize continuously three times or more.
Moreover, when grind | pulverizing twice or more, each grinder may be the same or different. It is also possible to use different types of pulverizers in combination.

For example, in order to control the crosslinked product of the present invention to a specific particle size distribution, a classification step and a granulation step may be provided. For the classification, a sieve with a specific opening may be used. The classifier used for classification with a sieve is not particularly limited. For example, a vibration sieve (unbalance weight drive type, resonance type, vibration motor type, electromagnetic type, circular vibration type, etc.), in-plane motion sieve (Horizontal motion type, horizontal circle-linear motion type, three-dimensional circular motion type, etc.), movable screen type screen, forced stirring screen, screen vibration screen, wind screen, sonic screen, etc. are used, preferably vibration screen An in-plane motion sieve is used.

When the crosslinked product of the present invention has a crosslinked structure formed by the above (2) to (5), in the method for producing the crosslinked product, the crosslinking is performed after performing a polymerization step for polymerizing monomer components. A post-crosslinking step will be performed to form the structure.
Examples of the method of post-crosslinking in the post-crosslinking step (crosslinking after polymerization) include, for example, (i) a method of irradiating the N-vinyl lactam polymer obtained in the polymerization step with UV, γ rays, and an electron beam, ( ii) a method of adding a reaction accelerator such as a condensing agent to the N-vinyl lactam polymer obtained in the polymerization step for self-crosslinking, and (iii) heating the N-vinyl lactam polymer obtained in the polymerization step. (Iv) A method in which a radical generator is contained in the N-vinyl lactam polymer obtained in the polymerization step and then self-crosslinking by adding heat, (v) obtained in the polymerization step Examples thereof include a method in which the obtained N-vinyl lactam polymer contains a radical polymerizable crosslinking agent (crosslinkable monomer) and a radical polymerization initiator, followed by heating and / or light irradiation.
In addition, as a polymer used for a post-crosslinking process, what was manufactured from the monomer component may be used and a commercially available polymer may be used.

When the crosslinked product of the present invention has the crosslinked structure formed by the above (2), the amount of the crosslinking agent used is the reactive functional group (reactive functional group that reacts with the crosslinking agent) of the polymer 100. The amount is preferably such that the functional group of the cross-linking agent is 30 to 100 mol% with respect to mol%. More preferably, it is 50-100 mol%. By using a crosslinking agent at such a ratio, a sufficient crosslinked structure can be formed, and the amount of unreacted crosslinking agent remaining in the resulting crosslinked product can be reduced.

Examples of the reaction accelerator used in the method (ii) include acids such as sulfuric acid and phosphoric acid; bases such as sodium hydroxide and potassium hydroxide; condensing agents such as N, N′-dicyclohexylcarbodiimide and the like. More than seeds can be used.
As the radical generator used in the method (iv), the same polymerization initiator as that used in the polymerization step described above can be used. Among the polymerization initiators, hydrogen peroxide, t-butyl hydroperoxide, t-butyl peroxypivalate, octanoyl peroxide, succinic peroxide, t-hexylperoxy-2-ethylhexanoate, t- Peroxides such as butyl peroxy-2-ethylhexanoate, t-butyl peroxyisobutyrate, and t-butyl peroxymaleic acid are preferred.

When the crosslinked product of the present invention has the crosslinked structure formed by the above (5), the amount of the crosslinking monomer used in the post-crosslinking is 100% by mass of the polymer before the post-crosslinking step. It is preferable that it is 0.1-50 mass% with respect to. More preferably, it is 1-30 mass%. By using a crosslinkable monomer at such a ratio, a sufficient crosslinked structure can be formed, and the amount of unreacted crosslinkable monomer remaining in the resulting crosslinked product can be reduced. it can.

<Surfactant support>
As described above, the surfactant-supporting agent (I) of the present invention includes the crosslinked product (I) of the present invention. The surfactant-supporting agent (I) of the present invention may contain only the crosslinked product (I) of the present invention, but may contain other components.
The surfactant-carrying agent (I) of the present invention contains the crosslinked product (I) of the present invention, for example, 10% by mass or more and 100% by mass or less with respect to 100% by mass of the surfactant-carrying agent (I). Also good. Preferably, it contains 50 mass% or more and 99.8 mass% or less.

The surfactant-supporting agent (I) of the present invention preferably has a water content of 0.1 to 5% by mass with respect to 100% by mass of the surfactant-supporting agent (I). More preferably, they are 1 mass% or more and 4 mass% or less, More preferably, they are 2 mass% or more and 4 mass% or less. By being in the above range, the surfactant-absorbing ability of the surfactant-carrying agent of the present invention tends to be improved, and the handleability tends to be improved. In addition, the water content of a crosslinked body is measured by the method mentioned later.
Even in the case where the surfactant-carrying agent (I) of the present invention contains only the crosslinked product (I) of the present invention, the water content in the surfactant-carrying agent is preferably within the above range. That is, the water content in 100% by mass of the crosslinked product (I) of the present invention is also preferably in the above range.

The surfactant-supporting agent (I) of the present invention preferably has an iron content of 0 to 50 ppm with respect to 100% by mass of the surfactant-supporting agent (I). More preferably, they are 0 ppm or more and 40 ppm or less, More preferably, they are 0 ppm or more and 30 ppm or less. By being in the above range, color tone and storage stability tend to be good. The iron content is evaluated by the method described later.
Even in the case where the surfactant-carrying agent (I) of the present invention contains only the crosslinked product (I) of the present invention, the iron content in the surfactant-carrying agent is preferably within the above range. That is, the iron content in 100% by mass of the crosslinked product (I) of the present invention is also preferably in the above range.
In order to make the content of iron in the above range, it is preferable to use a polymerization initiator other than iron-containing polymerization initiator as a polymerization initiator in producing the crosslinked product (I) of the present invention. It is preferable to use a reaction vessel made of a material that does not elute iron.

In the surfactant carrier (I) of the present invention, the content of N-vinyl lactam is preferably 1 to 1000 ppm with respect to 100% by mass of the surfactant carrier (I). More preferably, they are 1 ppm or more and 800 ppm or less, More preferably, they are 1 ppm or more and 500 ppm or less. By being in the above range, color tone and storage stability tend to be good. Moreover, since the high safety | security is calculated | required by the material used for cosmetics use, when the content of N-vinyl lactam is the said range, the surfactant carrying | support agent (I) of this invention is more safe. It is high and becomes more suitable as a material used for cosmetics.
Also in the case where the surfactant-carrying agent (I) of the present invention contains only the crosslinked product (I) of the present invention, the content of N-vinyllactam in the surfactant-carrying agent is preferably within the above range. . That is, the N-vinyl lactam content in 100% by mass of the crosslinked product (I) of the present invention is also preferably in the above range.

The surfactant-supporting agent (I) of the present invention preferably has a surfactant absorbing capacity of 10 g / g or more (that is, 10 times or more). More preferably, it is 15 g / g or more (that is, 15 times or more), and further preferably 20 g / g or more (that is, 20 times or more). The upper limit of the liquid absorption capacity of the surfactant is, for example, 50 g / g or less (that is, 50 times or less).
Even in the case where the surfactant-carrying agent (I) of the present invention contains only the crosslinked product (I) of the present invention, the liquid-absorbing ability of the surfactant-carrying agent is preferably within the above range. That is, the liquid absorption capacity of the crosslinked product (I) of the present invention is also preferably in the above range.

The second surfactant-carrying agent of the present invention (hereinafter also referred to as “surfactant-carrying agent (II)”) preferably has a liquid absorption capacity of the surfactant of 10 g / g or more (that is, 10 times or more). Is a surfactant carrier of 15 g / g or more (that is, 15 times or more), more preferably 20 g / g or more (that is, 20 times or more).
The surfactant-carrying agent (II) of the present invention may be the surfactant-carrying agent (I), but the cyclic N-vinyllactam-based crosslinked product in the surfactant-carrying agent (I) is converted to (meth) acrylic. A surfactant-supporting agent replaced with a dimethylaminoethyl acid-based crosslinked product may be used.

The surfactant-carrying agent of the present invention may be used in powder form, but may be used by dispersing in a dispersion medium and using as a dispersion, or carrying it on a film or the like and forming it into a sheet form. The content of the surfactant-supporting agent of the present invention contained in the dispersion or the entire sheet can be set to 1% by mass to 80% by mass, for example.

The surfactant-carrying agent of the present invention is used for loading a surfactant, and the surfactants that can be carried are nonionic surfactants, anionic surfactants, cationic surfactants, amphoteric surfactants. Alternatively, polymer surfactants, reactive surfactants and the like can be mentioned, but there is no particular limitation. The surfactant-supporting agent of the present invention is particularly preferably used for supporting an anionic surfactant among the above-mentioned surfactants.

Examples of the anionic surfactant include alkylbenzene sulfonic acid (salt), alkyl sulfate, polyoxyethylene alkyl sulfate, alkane sulfonic acid (salt), polyoxyethylene alkyl ether methyl carboxylic acid (salt), linoleic acid, Examples include higher fatty acids such as oleic acid and salts thereof.

Nonionic surfactants include, for example, polyoxyethylene alkyl ethers, polyoxyethylene alkyl aryl ethers, sorbitan fatty acid esters, polyoxyethylene sorbitan fatty acid esters, fatty acid monoglycerides such as glycerol monolaurate, polyoxyethylene-polyoxypropylene, and the like. Examples thereof include copolymers.

Examples of amphoteric surfactants include N-acylamidopropyl-N, N-dimethylammoniobetaine, N-acylamidopropyl-N ′, N′-dimethyl-N′-β-hydroxypropylammoniosulfobetaine, and the like. And examples of the cationic surfactant include monoalkyltrimethylammonium methosulfate and cationized cellulose.

The surfactant-carrying agent of the present invention may carry the above-mentioned surfactant alone or may carry two or more kinds.

When using the surfactant-carrying agent of the present invention, a surfactant that does not carry (absorb) a surfactant may be used, but a surfactant or a solvent compatible with the surfactant is carried in advance. It is preferable to use a surfactant carrying agent, and the use of such a surfactant carrier makes it possible to increase the rate of absorbing the surfactant.
As described above, the surfactant-supporting agent of the present invention is that in which a surfactant and / or a solvent that is compatible with the surfactant is previously supported, is a preferred form of the surfactant-supporting agent of the present invention. One.
In addition, a method of using a surfactant-supporting agent of the present invention in which a surfactant and / or a solvent compatible with the surfactant is previously supported is used as a surfactant absorbent. It is.
Furthermore, a polymerization step of polymerizing a monomer component containing N-vinyl lactam to obtain a cyclic N-vinyl lactam cross-linked product, a cyclic N-vinyl lactam cross-linked product obtained in the polymerization step with a surfactant and A method for producing a surfactant absorbent comprising a step of supporting a solvent compatible with the surfactant is also one aspect of the present invention. In the method for producing an absorbent material, the polymerization step for polymerizing a monomer component containing N-vinyl lactam to obtain a cyclic N-vinyl lactam-based crosslinked product includes the above-described method for producing the crosslinked product (I) of the present invention. It is preferable to carry out similarly.

As described above, the surfactant-carrying agent of the present invention has a good ability to adsorb and retain a surfactant, and can be used in cosmetics. When using the surfactant support agent of the invention, it is easy to absorb the surfactant support agent by using a surfactant support agent in which a surfactant or a solvent compatible with the surfactant is previously supported. Thus, more surfactant can be absorbed by the surfactant carrier. Such a surfactant absorbent for cosmetics, in which a surfactant or a solvent compatible with the surfactant is previously carried on the first or second surfactant carrier of the present invention, that is, the surfactant A surfactant absorbent for cosmetics in which a surfactant or a solvent compatible with the surfactant is supported on 100% by mass of the surfactant-carrying agent having an agent absorbing capacity of 10 times or more of the weight of the carrier; and A cyclic N-vinyllactam-based crosslinked product, and the cyclic N-vinyllactam-based crosslinked product contains 50 to 100 mol% of structural units derived from N-vinyllactam, with respect to 100% by mass of the surfactant-supporting agent. A surfactant absorbent for cosmetics carrying a surfactant or a solvent compatible with the surfactant is also one aspect of the present invention.

The amount of the surfactant or the solvent compatible with the surfactant previously supported on the surfactant-carrying agent of the present invention is 0.01% by mass or more and 3% by mass with respect to 100% by mass of the surfactant-carrying agent. The following is preferable. When supported at such a ratio, the surfactant can absorb a sufficient amount of the surfactant while sufficiently exhibiting the action of absorbing the surfactant or the solvent compatible with the surfactant in advance. It can be an agent carrier. The amount of the surfactant or the solvent compatible with the surfactant previously supported is more preferably 0.1% by mass or more and 3% by mass or less with respect to 100% by mass of the surfactant-carrying agent. More preferably, it is 5 mass% or more and 3 mass% or less.

The surfactant to be previously supported on the surfactant carrier and the solvent compatible with the surfactant are not particularly limited as long as it is a solvent compatible with the surfactant or surfactant. C2-12 lower to intermediate fatty acids are preferred. More preferred are lower to higher fatty acids such as linoleic acid and oleic acid that are liquid at 25 ° C. to 45 ° C. under normal pressure (1 atm).

Since the surfactant supported on the surfactant support of the present invention is expected to have an effect of dispersing the hydrophobic component in the aqueous solvent, the surfactant support of the present invention is added to cosmetics containing the aqueous solvent. By doing so, an effect as a dispersant for the hydrophobic component in the cosmetic component can also be expected. In this case, the surfactant-carrying agent of the present invention may be added to cosmetics as it is, and the surfactant-carrying agent of the present invention is preliminarily supported with a surfactant or a solvent compatible with the surfactant. However, from the viewpoint of sufficiently exerting the effect as a dispersant, it is preferable to add a surfactant-supported agent previously supported by a surfactant to cosmetics.
In addition, when a cosmetic containing the surfactant-carrying agent of the present invention is applied to the human body, it is also expected that the water absorbed by the surfactant-carrying agent is gradually released to exert a moisturizing function.

Cosmetics using the surfactant carrier of the present invention are not particularly limited. For example, cosmetics for finishing such as makeup base, foundation, lipstick, etc .; cosmetics for skin such as lotion, emulsion, sunscreen, face wash; It can be used for any cosmetics such as cosmetics for hair.

The present invention will be described in more detail with reference to examples below, but the present invention is not limited to these examples.

<Method for evaluating surfactant absorption ability>
About 0.1 g of the crosslinked polymer was accurately weighed (mass W1 (g)), placed in a 4 cm × 5 cm non-woven tea bag, and sealed by heat sealing. The tea bag was immersed in linoleic acid as a surfactant at room temperature. After 24 hours, the tea bag was pulled up, placed on a Kim Towel (manufactured by Nippon Paper Crecia Co., Ltd.) and drained for 10 seconds, and then the mass (W2 (g)) of the tea bag was measured. Separately, the same operation was performed without using a crosslinked polymer, and the mass (W0 (g)) of the tea bag at that time was determined as a blank. The liquid absorption capacity calculated according to the following formula was defined as the surfactant absorption capacity.
Liquid absorption ratio (g / g) = (W2 (g) −W0 (g)) / W1 (g)
<Measurement method of average particle diameter>
The sieves were combined from the top in descending order of the openings, the crosslinked polymer was put on the uppermost sieve, and the mixture was shaken for 10 minutes with a micro-type electromagnetic vibration sieve device (M-2 type, manufactured by Tsutsui Rika Kikai Co., Ltd.). After measuring the mass of the mixture remaining on each sieve, the size of each sieve opening and the particles that could not pass through the sieve (particles remaining on the sieve and particles remaining on the larger sieve) The mass ratio (residual percentage) R to the whole of the total is plotted on a semi-logarithmic graph (horizontal axis: particle diameter (logarithmic scale), vertical axis: residual percentage), and the particle diameter corresponding to R = 50% is plotted. The average particle diameter was determined.

<Measurement method of iron content>
Using a fluorescent X-ray apparatus Philips PW2404 (manufactured by Panallytical), the Fe ion concentration of the crosslinked polymer was quantitatively analyzed, and the content of iron was determined.
The X-ray source of the fluorescent X-ray apparatus was Rh, the output was 60 kV, and the current value was 66 mA. The measurement range was 55.5 ° to 59.5 °, and the measurement was performed in a He atmosphere.
Calculation was performed by comparing the intensity of fluorescent X-rays of Fe-K rays between a sample with a known Fe concentration and a crosslinked polymer sample.

<Method for measuring water content>
In the cross-linked polymer, the proportion of components that volatilize at 150 ° C. is expressed as the water content. The relationship with the solid content is as follows.
Water content (mass%) = 100-solid content (mass%)
The solid content was measured as follows.
About 1 g of the crosslinked polymer is weighed (mass W4 (g)) in a weighing can (mass W3 (g)) having a bottom diameter of about 5 cm, and left to stand in a windless dryer at 150 ° C. for 1 hour, followed by drying. Let
The weight (W5 (g)) of the weighed can and the crosslinked polymer after drying was measured, and the solid content was determined from the following formula.
Solid content (mass%) = ((W5 (g) −W3 (g)) / W4 (g)) × 100
<Method for measuring N-vinyl lactam monomer content>
About 1.0 g of a polymer (mass W6 (g)) and about 100 g of deionized water (mass W7 (g)) were weighed and sealed in a 110-ml screw tube containing a rotor. Thereafter, the mixture was stirred at a room temperature for 16 hours or more using a magnetic stirrer (rotation speed: 600 rpm). By the above operation, the residual N-vinyl lactam monomer of the particulate crosslinked polymer was extracted. This extract was quantitatively analyzed with a liquid chromatograph under the following conditions.
Equipment: Shiseido “NANOSPACE SI-2”
Column: Shiseido “CAPCELLLPAK C18 UG120”, 20 ° C.
Eluent: LC methanol (manufactured by Wako Pure Chemical Industries, Ltd.) / Ultra pure water = 1/24 (mass ratio), 1-heptanesulfonic acid sodium 0.4 mass% addition flow rate: 100 μL / min
N-vinyl lactam content (ppm) = measured value (ppm) × (W6 (g) + W7 (g)) / W6 (g)

<Example 1>
50 parts of N-vinylpyrrolidone (manufactured by Nippon Shokubai Co., Ltd.) (hereinafter also referred to as VP), 0.2 part of triallyl cyanurate (hereinafter also referred to as CTA) as a crosslinkable monomer (0.18 mol% relative to VP) ), 117 parts of deionized water was charged into a 250 ml polypropylene (hereinafter also referred to as “PP”) container. Next, stirring was started with a magnetic stirrer, and nitrogen substitution was performed at 100 ml / min for 30 minutes. Subsequently, it heated up to 56 degreeC, continuing stirring. After stabilizing the liquid temperature at 56 ° C., 10% of 2,2′-azobis [2- (2-imidazolin-2-yl) propane] dihydrochloride (hereinafter also referred to as “VA-044”) was used as an initiator. 1.13 parts of a mass% aqueous solution (0.25 g with respect to 1 mol of the total amount of VP and CTA used) was added to initiate polymerization. After the polymerization reaction progressed and a gel was formed, aging was performed at 90 ° C. for 30 minutes to complete the polymerization. The obtained gel was crushed with a table kneader (PNV-1H type manufactured by Chuo Rika Co., Ltd.) and dried at 120 ° C. for 2 hours to obtain a dried VP cross-linked polymer. Subsequently, the obtained cross-linked polymer was pulverized with a pulverizer until it passed through a JIS standard sieve having an opening of 38 μm to obtain a particulate VP cross-linked polymer 1 (surfactant carrier (1) of the present invention). It was.
The surfactant carrier (1) of the present invention had a VP content of 500 ppm and an iron content of 10-15 ppm.
Next, with respect to the VP cross-linked polymer 1 (surfactant-carrying agent (1) of the present invention), the liquid absorption capacity, average particle diameter, and water content of the surfactant were measured according to the measurement methods described above. Table 1 shows the various performances measured.

<Example 2>
Desktop type made of 130.0 parts of VP, 0.52 parts of CTA as a crosslinkable monomer (0.18 mol% with respect to VP), 304.6 parts of deionized water, and main body tank made of stainless steel (SUS304) A kneader (PNV-1H type, manufactured by Chuo Rika Co., Ltd.) was used. Subsequently, nitrogen substitution was performed at 100 ml / min for 30 minutes. Next, nitrogen was introduced at 30 ml / min, and the temperature was raised to 56 ° C. After the liquid temperature was stabilized at 56 ° C., 1.96 parts of a 15 mass% aqueous solution of VA-044 (0.25 g based on 1 mol of the total amount of VP and CTA) was added as an initiator to initiate polymerization. did. After the polymerization reaction progressed and a gel was formed, aging was performed at 90 ° C. for 60 minutes while crushing the gel by rotating a kneader blade to complete the polymerization. Subsequently, the obtained gel was dried at 120 ° C. for 2 hours to obtain a dried VP cross-linked polymer. Next, the obtained cross-linked polymer was pulverized with a pulverizer until it passed through a JIS standard sieve having an opening of 100 μm, and particulate VP cross-linked polymer 2 (surfactant carrier (2) of the present invention) was obtained. Obtained.
The surfactant carrier (2) of the present invention had a VP content of 350 ppm and an iron content of 10 to 15 ppm.
Next, various physical properties (surfactant absorption capacity, average particle diameter, moisture content) of the VP crosslinked polymer 2 (surfactant carrier (2) of the present invention) by the same measurement method as in Example 1. Amount) was measured. Table 1 shows the various performances measured.

<Example 3>
1. 130.0 parts of VP, pentaerythritol triallyl ether (trade name: Neoallyl P-30M, manufactured by Daiso Co., Ltd., diethanolamine (manufactured by Nippon Shokubai Co., Ltd.) as a crosslinking monomer) 95 parts (0.65 mol% with respect to VP), 307.9 parts of deionized water, and a tabletop kneader (PNV-1H type manufactured by Chuo Rika Co., Ltd.) were charged. Subsequently, nitrogen substitution was performed at 100 ml / min for 30 minutes. Next, nitrogen was introduced at 30 ml / min and the temperature was raised to 60 ° C. After the liquid temperature was stabilized at 60 ° C., a 15% by mass aqueous solution of 2,2′-azobis (2-methylpropionamidine) dihydrochloride (hereinafter also referred to as “V-50”) as an initiator was added to 3.52 Part (0.45 g with respect to 1 mol of the total amount used of VP and pentaerythritol triallyl ether) was added to initiate polymerization. After the polymerization reaction progressed and a gel was formed, aging was performed at 90 ° C. for 60 minutes while crushing the gel by rotating a kneader blade to complete the polymerization. Subsequently, the obtained gel was dried at 120 ° C. for 2 hours to obtain a dried VP cross-linked polymer. Next, the obtained crosslinked polymer was pulverized with a pulverizer until it passed through a JIS standard sieve having an opening of 100 μm, and the particulate VP crosslinked polymer 3 (surfactant carrier (3) of the present invention) was obtained. Obtained.
The surfactant carrier (3) of the present invention had a VP content of 950 ppm and an iron content of 5-10 ppm.
Next, various physical properties of the VP crosslinked polymer 3 (surfactant carrier (3) of the present invention) were measured by the same measurement method as in Example 1. Table 1 shows the various performances measured.

<Comparative Example 1>
90 parts of 2-hydroxyethyl acrylate (manufactured by Nippon Shokubai Co., Ltd.) (hereinafter also referred to as HEA) containing 0.2% by mass of ethylene glycol diacrylate as impurities and 209 parts of deionized water are charged into a 600 ml PP container. It is. Next, stirring was started with a magnetic stirrer, and nitrogen substitution was performed at 100 ml / min for 30 minutes. Subsequently, it heated up to 40 degreeC, continuing stirring. After the liquid temperature was stabilized at 40 ° C., 1.12 parts of a 20% by weight aqueous solution of V-50 was added as an initiator to initiate polymerization. After the polymerization reaction progressed and a gel was formed, aging was performed at 90 ° C. for 30 minutes to complete the polymerization. The obtained gel was crushed with a table kneader (PNV-1H type, manufactured by Chuo Rika Co., Ltd.) and dried at 120 ° C. for 2 hours to obtain a dried HEA crosslinked polymer. Next, the obtained crosslinked product was pulverized and classified with a pulverizer to obtain a HEA crosslinked polymer (Comparative Crosslinked Polymer 1). Various physical properties were measured by the same measurement method as in Example 1. Table 1 shows the various performances measured.

<Comparative example 2>
30 parts of HEA containing 0.2% by mass of ethylene glycol diacrylate as impurities, 12.3 parts of VP, 0.05 part of CTA as crosslinkable monomer, and 98.8 parts of deionized water were charged into a 250 ml PP container. Next, stirring was started with a magnetic stirrer, and nitrogen substitution was performed at 100 ml / min for 30 minutes. Subsequently, it heated up to 50 degreeC, continuing stirring. After the liquid temperature was stabilized at 50 ° C., 1.5 parts of a 10% by mass aqueous solution of V-50 as an initiator was added to initiate polymerization. After the polymerization reaction progressed and a gel was formed, aging was performed at 90 ° C. for 30 minutes to complete the polymerization. The obtained gel was crushed with a table kneader (PNV-1H type, manufactured by Chuo Rika Co., Ltd.) and dried at 120 ° C. for 2 hours to obtain a dried HEA / VP crosslinked polymer. Next, the obtained crosslinked product was pulverized and classified with a pulverizer to obtain a HEA / VP crosslinked polymer (comparative crosslinked polymer 2). Various physical properties were measured by the same measurement method as in Example 1. Table 1 shows the various performances measured.

<Comparative Example 3>
In a flask equipped with a reflux condenser, thermometer, nitrogen gas inlet tube, TK homogenizer (stirrer, manufactured by Tokushu Kika Kogyo Co., Ltd.), etc., polyoxyethylene alkyl sulfoammonium (first) as a dispersion stabilizer An aqueous solution prepared by dissolving 0.5 part of Koyo Pharmaceutical Co., Ltd., trade name: Hytenol N-08) in 400 parts of deionized water was charged. On the other hand, a monomer composition containing 99.5 parts of stearyl acrylate and 0.5 parts of ethylene glycol methacrylate (hereinafter also referred to as EGDMA) as a crosslinkable monomer, and a peroxidation as a polymerization initiator (organic peroxide). A mixture formed by mixing 1.0 part of lauroyl oxide was prepared. And after adding the said mixture to the aqueous solution in a flask, the uniform suspension was obtained by stirring the contents vigorously for 5 minutes at a rotational speed of 4000 rpm. Next, the suspension was heated to 75 ° C. while nitrogen gas was blown into the flask, and a radical polymerization reaction was performed with stirring at the same temperature for 2 hours to obtain a fine particle dispersion. Next, the fine particle dispersion was subjected to solid-liquid separation by natural sedimentation. The obtained cake was dried with hot air at 50 ° C. for 10 hours to obtain an oil-absorbing resin (Comparative Crosslinked Polymer 3). Various physical properties were measured by the same measurement method as in Example 1. Table 1 shows the various performances measured. However, the average particle size of the comparative crosslinked polymer 3 was calculated from the volume-based particle size distribution obtained by measuring the volume-based particle size distribution using a Multisizer III Coulter Counter (manufactured by Beckman Coulter, Inc.).

<Comparative example 4>
A commercially available polyacrylic acid-based liquid-absorbing resin (manufactured by Nippon Shokubai Co., Ltd., trade name: Aqualic CA, hereinafter referred to as comparative crosslinked polymer 4), which is a conventional liquid-absorbing resin, is the same as in Example 1. Various physical properties were measured by measurement methods. The comparative crosslinked polymer 4 was pulverized and classified in the same manner as in Example 1, and the average particle diameter was made uniform with that of the VP crosslinked polymer.

The evaluation results of the VP crosslinked polymers obtained in Examples 1 to 3 of the present invention and the comparative crosslinked polymers obtained in Comparative Examples 1 to 4 are summarized in Table 1.

From the results in Table 1, it was revealed that the surfactant-carrying agent of the present invention has a good surfactant carrying property.

<Example 4>
The surfactant-supporting agent (1) of the present invention obtained in Example 1 and an interface previously swollen with linoleic acid three times ((supporting agent weight + absorbed linoleic acid) / supporting agent weight = 3). The linoleic acid absorption rate of the activator carrier (1) was measured.
(Measurement method of surfactant absorption rate)
About 0.1 g of VP cross-linked polymer (when linoleic acid as a surfactant is previously supported, the amount of VP cross-linked polymer is about 0.1 g) is accurately weighed (mass W8 (g)), 4 cm × It was put in a 5 cm non-woven tea bag and sealed by heat sealing. The tea bag was immersed in linoleic acid at room temperature. At three points between 0.5 and 2 hours, the tea bag was pulled up, placed on a Kim towel (Nippon Paper Crecia Co., Ltd.) and drained for 10 seconds, and then the mass of the tea bag (W9 (g )) Was measured. Separately, the same operation was performed without using a crosslinked polymer, and the mass (W10 (g)) of the tea bag at that time was determined as a blank. The liquid absorption capacity calculated according to the following formula was defined as the surfactant liquid absorption capacity.
Liquid absorption ratio (g / g) = (W9 (g) -W10 (g)) / W8 (g)
Table 2 shows the results of elapsed time and surfactant absorption ratio.

From the results shown in Table 2, it has been clarified that when the surfactant-carrying agent of the present invention is swollen three times with linoleic acid in advance, the liquid absorption speed is remarkably improved.

<Example 5>
When the surfactant-supporting agent of the present invention in which a surfactant (linoleic acid) is previously absorbed is mixed with a mixed solution of water and a solvent (mixing 1), A case where the surfactant-supporting agent of the present invention in which the activator was not absorbed was mixed with a mixed solution of water and a solvent (formulation 2) was compared as follows.
(Formulation 1)
1 g of linoleic acid was absorbed into 1 g of the surfactant-supporting agent (1) of the present invention obtained in Example 1 (the linoleic acid absorption rate of the surfactant-supporting agent (1) was doubled). Next, 2 g of the surfactant-carrying agent (1) in which linoleic acid was absorbed was added to a mixed liquid (mass ratio 1: 1) of 50 g of liquid paraffin and 50 g of deionized water to obtain a mixed solution (1).
(Evaluation of mixed solution (1))
The increase in mass of the surfactant-carrying agent (1) after leaving the mixed solution (1) at room temperature for 24 hours was 9 g (change from 2 g to 11 g). The increase in weight was due to the absorption of deionized water.
10 g of linoleic acid was added to the mixed solution (1) after being allowed to stand at room temperature for 24 hours, and then allowed to stand at room temperature for 5 hours. The increase in mass of the surfactant-carrying agent (1) after standing was 10 g. The increase in weight was due to the absorption of linoleic acid.

(Formulation 2)
1 g of the surfactant-supporting agent (1) of the present invention was added to a mixed solution (mass ratio 1: 1) of 50 g of liquid paraffin and 50 g of deionized water to obtain a mixed solution (2).
(Evaluation of mixed solution (2))
The increase in mass of the surfactant-carrying agent (1) after leaving the mixed solution (2) at room temperature for 24 hours was 22 g (change from 1 g to 23 g).
10 g of linoleic acid was added to the mixed solution (2) after standing at room temperature for 24 hours and allowed to stand at room temperature for 5 hours. There was no increase in the mass of the surfactant-carrying agent (1) after standing.

From the above results, the surfactant support agent (1) is preliminarily supported with linoleic acid as a surfactant, as in the mixed solution (1), so that the surfactant support agent can be used even in a mixture of water and a solvent. It became clear that (1) can absorb the surfactant.

Claims (7)

Surfactant carrying agent having a surfactant absorption capacity of 10 times or more. A surfactant-supporting agent comprising a cyclic N-vinyllactam-based crosslinked product, wherein the cyclic N-vinyllactam-based crosslinked product has 50 to 100 mol% of structural units derived from N-vinyllactam. The surfactant carrier according to claim 1 or 2, wherein the content of N-vinyl lactam is 1-1000 ppm with respect to 100% by mass of the surfactant carrier. The surfactant carrier according to any one of claims 1 to 3, wherein the iron content is 50 ppm or less with respect to 100% by mass of the surfactant carrier. The surfactant-carrying agent according to any one of claims 1 to 4, wherein the average particle size is 0.1 to 100 µm. The surfactant carrier according to any one of claims 1 to 5, wherein the water content is 0.1 to 5% by mass with respect to 100% by mass of the surfactant carrier. The surfactant carrier according to any one of claims 1 to 6, which is a carrier for an anionic surfactant.